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CN1382164A - Copolymers of aminopropyl vinyl ether - Google Patents

Copolymers of aminopropyl vinyl ether Download PDF

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Publication number
CN1382164A
CN1382164A CN00814780A CN00814780A CN1382164A CN 1382164 A CN1382164 A CN 1382164A CN 00814780 A CN00814780 A CN 00814780A CN 00814780 A CN00814780 A CN 00814780A CN 1382164 A CN1382164 A CN 1382164A
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substrate
antimicrobial polymer
antimicrobial
vinyl ether
methacrylate
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P·奥特斯巴赫
B·科斯曼
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CREVIS TECHNOLOGY AND CREATION Co Ltd
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CREVIS TECHNOLOGY AND CREATION Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14Monomers containing only one unsaturated aliphatic radical
    • C08F216/1458Monomers containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/18Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to irradiated or oxidised macromolecules
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention relates to antimicrobial polymers which can be obtained by copolymerizing vinyl ethers of general formula (I), especially 3-aminopropyl vinyl ethers, with additional aliphatically unsaturated monomers, and to a method for the production thereof. The polymers can also be produced by graft copolymerizing a substrate, whereby a covalently bound coating is obtained on the surface of the substrate. The antimicrobial polymers can be used as a microbicide coating, among other things, on hygiene articles or in the field of medicine, as well as in paints or protective paint coatings.

Description

氨丙基乙烯基醚的共聚物Copolymer of aminopropyl vinyl ether

本发明涉及通过氨基官能化乙烯基醚与其它单体共聚获得的抗微生物聚合物。本发明进一步涉及制备这些抗微生物聚合物的方法和其用途。The present invention relates to antimicrobial polymers obtained by copolymerization of amino-functionalized vinyl ethers with other monomers. The invention further relates to processes for the preparation of these antimicrobial polymers and their use.

本发明还涉及通过将氨基官能化乙烯基醚与其它单体在基物上接枝共聚获得的抗微生物聚合物,涉及制备这些接枝共聚物的方法和其用途。The invention also relates to antimicrobial polymers obtained by graft copolymerization of amino-functionalized vinyl ethers with other monomers on substrates, to processes for the preparation of these graft copolymers and to their use.

特别不希望细菌在管线、容器或包装物表面上繁殖生长和蔓延。常常形成烂泥层(Schleimschichten)且会使微生物群体急剧增加,这些会导致对水、饮料和食品质量的持续危害,甚至使产品变质并损害消费者健康。The growth and spread of bacteria on the surfaces of lines, containers or packaging is particularly undesirable. Sludge layers are often formed and the microbial population can increase dramatically, which can lead to continuous damage to the quality of water, beverages and food, and even spoil the products and damage the health of consumers.

细菌必须远离其中卫生是重要的所有生活区域。这影响直接身体接触(尤其是生殖区域)的织物,和对老人和病人护理的织物。细菌还必须远离病房中的、特别是医院的加强护理和新生儿护理区域中的、尤其是医疗应急区域中的,和危险传染病的隔离病房中的以及洗手间的家具和仪器的表面。Germs must be kept away from all living areas where hygiene is important. This affects fabrics in direct body contact (especially the genital area), and fabrics for elderly and sick care. Germs must also be kept away from surfaces of furniture and instruments in wards, especially in intensive care and neonatal care areas of hospitals, especially in medical emergency areas, and in isolation wards for dangerous infectious diseases, as well as in washrooms.

目前处理装置,或家具和织物表面(当此变得必要或作为预防措施时)的方法是,使用作为消毒剂时具有相当广谱或常规杀微生物作用的化学品或其溶液或混合物。这类化学试剂非特异地起作用并且通常本身有毒性或刺激性,或形成对健康有害的降解产品。此外,一旦人们变敏感时,通常表现出对这些物质的不耐受性。The current method of treating fixtures, or furniture and fabric surfaces when this becomes necessary or as a precautionary measure, is to use chemicals or solutions or mixtures thereof which have a fairly broad spectrum or general microbicidal action as disinfectants. Such chemical agents act non-specifically and are often themselves toxic or irritating, or form degradation products that are harmful to health. Furthermore, once people become sensitized, they often show an intolerance to these substances.

抵抗细菌表面扩散的另一方法是将具有可微生物作用的物质加入基物中。Another way to counteract the spread of bacteria on surfaces is to incorporate microbiologically active substances into the substrate.

甲基丙烯酸叔丁氨基乙酯是甲基丙烯酸酯化学中可市购的单体,并特别用作共聚中的亲水性成份。例如,EP-PS 0 290 676描述了将各种聚丙烯酸酯和聚甲基丙烯酸酯作为抑制细菌的季铵化合物的基物。Tert-butylaminoethyl methacrylate is a commercially available monomer in methacrylate chemistry and is used especially as the hydrophilic component in copolymerizations. For example, EP-PS 0 290 676 describes various polyacrylates and polymethacrylates as bases for bacteriostatic quaternary ammonium compounds.

在另一技术领域,US-PS 4 532 269公开了甲基丙烯酸丁酯、甲基丙烯酸三丁基锡和甲基丙烯酸叔丁氨基乙酯的三元聚合物。此聚合物用作船舶的抗微生物漆,其中,该亲水性甲基丙烯酸叔丁氨基乙酯促进聚合物逐渐腐蚀,如此释放出高毒性甲基丙烯酸三丁基锡作为杀微生物物质。In another technical field, US-PS 4 532 269 discloses terpolymers of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate. This polymer is used as an antimicrobial paint for ships, where the hydrophilic tert-butylaminoethyl methacrylate promotes gradual corrosion of the polymer, thus releasing highly toxic tributyltin methacrylate as a microbicide.

在这些应用中,用氨基甲基丙烯酸酯制备的聚合物仅是用于加入杀微生物剂的基物或载体物质,该杀微生物剂会从载体物质中扩散或迁移出来。如果在表面上不再达到“最小的抑制浓度”(MIC)时,这类聚合物即或快或慢的丧失其效果。In these applications, the polymers prepared with aminomethacrylates are merely substrates or carrier materials for the addition of microbicides from which they diffuse or migrate. Such polymers lose their effect more or less quickly if the "minimum inhibitory concentration" (MIC) is no longer reached on the surface.

欧洲专利申请0 862 858和0 862 859公开了甲基丙烯酸叔丁氨基乙酯(一种具有仲氨基官能团的甲基丙烯酸酯)的均聚和共聚物具有内在的杀微生物性质。为避免微生物的不合适的耐受现象,特别是考虑到从抗菌素研究中已知的细菌形成的耐受现象,未来开发的体系还必须基于具有改进的效果的新组合物。European Patent Applications 0 862 858 and 0 862 859 disclose that homo- and copolymers of tert-butylaminoethyl methacrylate, a methacrylate with secondary amino functionality, have intrinsic microbicidal properties. In order to avoid unsuitable resistance phenomena of microorganisms, in particular in view of the resistance phenomena known from antimicrobial studies developed by bacteria, systems developed in the future must also be based on new compositions with improved efficacy.

因此,本发明目的是开发具有防止细菌在表面上繁殖和扩散的抗微生物作用的新聚合物。Therefore, the object of the present invention is to develop new polymers having an antimicrobial effect which prevents the multiplication and spread of bacteria on surfaces.

现在已令人吃惊地发现,将氨基官能化乙烯基醚与脂族不饱和单体共聚,和将这些组分在基物上接枝共聚,得到具有永久抗微生物、耐溶剂和物理应力且不呈现迁移的聚合物。这意味着不需要使用其它杀生物剂。It has now surprisingly been found that the copolymerization of amino-functionalized vinyl ethers with aliphatically unsaturated monomers, and the graft copolymerization of these components on the substrate, results in permanent antimicrobial, solvent and physical stress resistant Migrating polymers are present. This means that no other biocides need to be used.

3-氨丙基乙烯基醚为可市购的产品,其制备方法例如可在EP 0514,710中找到。它本身特别用作光刻胶体系的添加剂(例如描述于US 5648194中),或作为在特定氨基甲酸酯-硅烷中的粘结促进剂的结构成分(例如描述在US 5 384 342中)。这类化合物在抗微生物聚合物中的用途还不知道。3-Aminopropyl vinyl ether is a commercially available product, the preparation of which can be found, for example, in EP 0514,710. It is used in particular by itself as an additive to photoresist systems (for example as described in US 5648194), or as a structural component of adhesion promoters in specific urethane-silanes (for example as described in US 5 384 342). The use of such compounds in antimicrobial polymers is not known.

因此,本发明提供一种抗微生物共聚物,其通过将如下通式的乙烯基醚与至少一种脂族不饱和单体共聚获得,所述通式为:其中R1为具有1至5个碳原子的支化或未支化的烃基,和R2、R3为H或具有1至5个碳原子的支化或未支化的烃基,其中R2和R3可以相同或不同。Accordingly, the present invention provides an antimicrobial copolymer obtained by copolymerizing a vinyl ether of the general formula with at least one aliphatically unsaturated monomer: Wherein R 1 is a branched or unbranched hydrocarbon group with 1 to 5 carbon atoms, and R 2 , R 3 are H or a branched or unbranched hydrocarbon group with 1 to 5 carbon atoms, wherein R 2 and R3 may be the same or different.

为由该聚合物获得足够的抗微生物作用,乙烯基醚在反应混合物中的比例应为5至98mol%,优选30至98mol%,特别优选50至98mol%,按单体的总重量计。In order to obtain a sufficient antimicrobial effect from the polymers, the proportion of vinyl ether in the reaction mixture should be 5 to 98 mol %, preferably 30 to 98 mol %, particularly preferably 50 to 98 mol %, based on the total weight of the monomers.

使用的脂族不饱和单体可为进入与上述通式的乙烯基醚共聚中的任何单体。合适的单体的例子是丙烯酸酯或甲基丙烯酸酯,如丙烯酸、甲基丙烯酸叔丁酯或甲基丙烯酸甲酯、苯乙烯、氯乙烯、乙烯基醚、丙烯酰胺、丙烯腈、烯烃(乙烯、丙烯、丁烯或异丁烯)、烯丙基化合物、乙烯基酮、乙烯基乙酸、乙酸乙烯酯或乙烯基酯,特别是,例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸叔丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸叔丁酯、叔丁基氨基乙酯、甲基丙烯酸2-二乙氨基乙酯、2-二乙氨基乙基乙烯基醚、N-3-二甲氨基丙基甲基丙烯酰胺、3-甲基丙烯酰基氨丙基三甲基氯化铵、2-甲基丙烯酰氧基乙基三甲基氯化铵或2-甲基丙烯酰氧基乙基三甲基甲硫酸铵。The aliphatically unsaturated monomer used may be any monomer which enters into the copolymerization with the vinyl ether of the general formula above. Examples of suitable monomers are acrylates or methacrylates such as acrylic acid, tert-butyl or methyl methacrylate, styrene, vinyl chloride, vinyl ether, acrylamide, acrylonitrile, olefins (ethylene , propylene, butene or isobutene), allyl compounds, vinyl ketones, vinyl acetic acid, vinyl acetate or vinyl esters, especially, for example methyl methacrylate, ethyl methacrylate, butyl methacrylate ester, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butylaminoethyl, 2-diethylaminoethyl methacrylate, 2-diethylaminoethyl Vinyl ether, N-3-dimethylaminopropyl methacrylamide, 3-methacryloylaminopropyl trimethyl ammonium chloride, 2-methacryloyloxyethyl trimethyl chloride ammonium or 2-methacryloyloxyethyltrimethylammonium methosulfate.

脂族不饱和单体优选为丙烯酸化合物或甲基丙烯酸化合物,上述通式的乙烯基醚优选为3-氨丙基乙烯基醚。The aliphatic unsaturated monomer is preferably an acrylic compound or a methacrylic compound, and the vinyl ether of the above general formula is preferably 3-aminopropyl vinyl ether.

本发明的抗微生物共聚物可通过将上述通式的乙烯基醚(特别是3-氨丙基乙烯基醚)与一种或多种脂族不饱和单体共聚获得。聚合通常使用自由基引发剂或通过辐射诱导的自由基聚合。典型的工艺描述于这些实施例中。The antimicrobial copolymers of the present invention can be obtained by copolymerizing vinyl ethers of the general formula above (especially 3-aminopropyl vinyl ether) with one or more aliphatic unsaturated monomers. Polymerization typically uses free radical initiators or by radiation-induced free-radical polymerization. Typical processes are described in these examples.

本发明的抗微生物共聚物也可通过将上述通式的乙烯基醚(特别是3-氨丙基乙烯基醚)与至少一种脂族不饱和单体在基物上共聚获得。如此得到在基物上的抗微生物共聚物的物理吸附涂层。The antimicrobial copolymers according to the invention can also be obtained by copolymerizing vinyl ethers of the above general formula (in particular 3-aminopropyl vinyl ether) with at least one aliphatically unsaturated monomer on the substrate. This results in a physisorbed coating of the antimicrobial copolymer on the substrate.

合适的基物材料特别为所有的聚合物塑料,如聚氨酯、聚酰胺、聚酯或聚醚、聚醚嵌段酰胺、聚苯乙烯、聚氯乙烯、聚碳酸酯、聚有机硅氧烷、聚烯烃、聚砜、聚异戊二烯、聚氯丁二烯、聚四氟乙烯(PTFE)相应的共聚物和共混物,和天然的和合成的橡胶(有或无辐射敏感基团)。本发明方法可用于涂布的或其它用塑料涂层的金属、玻璃或木材的表面上。Suitable substrate materials are in particular all polymer plastics, such as polyurethane, polyamide, polyester or polyether, polyether block amides, polystyrene, polyvinyl chloride, polycarbonate, polyorganosiloxane, poly Corresponding copolymers and blends of olefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), and natural and synthetic rubbers (with or without radiation-sensitive groups). The method of the invention can be used on coated or otherwise plastic-coated metal, glass or wood surfaces.

在本发明另一实施方案中,这些共聚物可通过将基物与上述通式的乙烯基醚,特别是3-氨丙基乙烯基醚与至少一种脂族不饱和单体接枝聚合而制备。基物接枝可使抗微生物共聚物与基物共价连接。可使用的基物为任何聚合物材料,如上述塑料。In a further embodiment of the invention, these copolymers can be obtained by graft polymerizing the base with vinyl ethers of the general formula above, in particular 3-aminopropyl vinyl ether with at least one aliphatically unsaturated monomer preparation. Substrate grafting allows the covalent attachment of the antimicrobial copolymer to the substrate. Substrates that can be used are any polymeric material, such as the plastics mentioned above.

在接枝共聚之前,基物的表面可通过各种方法活化。这里可使用使聚合物表面活化的任何标准方法,例如在接枝聚合前可将基物通过UV辐射、等离子处理、电晕处理、火焰处理、臭氧处理、放电或γ-辐射等成熟方法活化。通常首先将这些表面按已知方式用溶剂除去油、脂或其它污染物。Before graft copolymerization, the surface of the substrate can be activated by various methods. Any standard method of surface activation of polymers can be used here, for example the substrates can be activated by UV radiation, plasma treatment, corona treatment, flame treatment, ozone treatment, electric discharge or gamma radiation etc. well established methods before graft polymerization. These surfaces are usually first solvent-freed of oil, grease or other contaminants in a known manner.

这些基材可用波长170至400nm、优选170至250nm范围内的UV射线活化。合适的射线源例如是购自HERAEUS,Hanau,Deutschland的Noblelight UV受激准分子仪器。然而,汞蒸气灯也适合基物活化,只要它们发射相当比例的上述范围内的射线即可。暴露时间通常为0.1秒至20分钟,优选1秒至10分钟。These substrates can be activated with UV radiation having a wavelength in the range from 170 to 400 nm, preferably from 170 to 250 nm. A suitable radiation source is eg the Noblelight UV excimer instrument from HERAEUS, Hanau, Deutschland. However, mercury vapor lamps are also suitable for substrate activation as long as they emit a substantial proportion of radiation within the above range. The exposure time is usually 0.1 second to 20 minutes, preferably 1 second to 10 minutes.

在接枝聚合前用UV射线活化基物也可用另外的光敏剂进行。例如,可将光敏剂如二苯甲酮涂于基材表面上然后照射。这里还可使用汞蒸气灯,其中暴露时间为0.1秒至20分钟,优选1秒至10分钟。Activation of the substrate with UV radiation prior to graft polymerization can also be carried out with additional photosensitizers. For example, a photosensitizer such as benzophenone can be applied to the surface of the substrate and then irradiated. Mercury vapor lamps can also be used here, with an exposure time of 0.1 second to 20 minutes, preferably 1 second to 10 minutes.

根据本发明,活化还可通过使用RF或微波等离子体(Hexagon,Technics Plasma,85551 Kirchheim,Deutschland)在空气、氮气或氩气气氛中进行等离子体处理实现。暴露时间通常为2秒至30分钟,优选5秒至10分钟。对于实验室装置,供给的能量为100至500W,优选200至300W。According to the invention, activation can also be achieved by plasma treatment in an air, nitrogen or argon atmosphere using RF or microwave plasma (Hexagon, Technics Plasma, 85551 Kirchheim, Deutschland). The exposure time is usually 2 seconds to 30 minutes, preferably 5 seconds to 10 minutes. For laboratory installations, the power supplied is from 100 to 500W, preferably from 200 to 300W.

还可将电晕装置(SOFTAL,Hamburg,Deutschland)用于活化。在此情况下暴露时间通常为1至10min,优选1至60秒。A corona device (SOFTAL, Hamburg, Deutschland) was also used for activation. The exposure time in this case is generally 1 to 10 min, preferably 1 to 60 seconds.

通过放电、电子束或γ-射线(例如来自钴60源的)以及臭氧化的活化可使暴露时间短短,通常为0.1至60秒。Activation by electric discharge, electron beam or gamma radiation (eg from a cobalt-60 source), and ozonation can result in short exposure times, typically 0.1 to 60 seconds.

基物表面也可通过火焰处理实现活化。合适的装置,特别是具有阻挡火焰面的那些,可容易装配或从ARCOTEC,71297 Mnsheim,Deutschland购买。它们可用烃或氢气作为燃烧气体操作。在所有情况下,必须避免因过热而损害基物,若远离火焰处理一侧的基物表面与冷却的金属表面紧密接触,则这容易确保。因此通过火焰处理进行的活化限于相当薄的片状基物。暴露时间通常为0.1秒至1分钟,优选0.5至2秒。火焰仅为无光的,基物表面与火焰前面外层的距离为0.2至5cm,优选0.5至2cm。The substrate surface can also be activated by flame treatment. Suitable devices, especially those with flame-resisting faces, are easily fitted or can be purchased from ARCOTEC, 71297 Mönsheim, Deutschland. They can be operated with hydrocarbon or hydrogen as combustion gas. In all cases, damage to the substrate by overheating must be avoided, which is easily ensured if the surface of the substrate on the side remote from the flame treatment is in intimate contact with the cooled metal surface. Activation by flame treatment is therefore limited to relatively thin sheet-like substrates. The exposure time is usually 0.1 second to 1 minute, preferably 0.5 to 2 seconds. The flame is only matt, the distance between the substrate surface and the outer layer in front of the flame is 0.2 to 5 cm, preferably 0.5 to 2 cm.

将按此方式活化的基物表面通过已知方法,如浸涂、喷涂或铺展,用上述通式的乙烯基醚(组分I),特别是3-氨丙基乙烯基醚并用一种或多种脂族不饱和单体(组分II),必要时在溶液中涂布。已证明合适的溶剂是水、乙醇和水/醇混合物,但其它溶剂也可以使用,只要足够溶解单体并实现基物表面的良好润湿即可。已证明具有单体含量1至10wt%,例如约5wt%的溶液在实际中是成功的,通常在一次通过时得到覆盖基物表面的粘结涂层,该涂层具有可大于0.1微米的厚度。The surface of the substrate activated in this way is treated with a vinyl ether (component I) of the above general formula, especially 3-aminopropyl vinyl ether, in combination with one or Various aliphatically unsaturated monomers (component II), if necessary coated in solution. Suitable solvents have proven to be water, ethanol and water/alcohol mixtures, but other solvents can be used as long as they are sufficient to dissolve the monomer and achieve good wetting of the substrate surface. Solutions having a monomer content of 1 to 10 wt%, e.g. about 5 wt%, have proven successful in practice, usually in one pass resulting in a bond coat covering the surface of the substrate with a thickness that can be greater than 0.1 microns .

施于活化表面的单体的接枝共聚通常可通过可见光范围的短波部分中的或电磁射线的UV范围的长波部分中的射线引发。例如,来自UV受激准分子的波长为250至500nm、优选290至320nm的射线非常合适。汞蒸气灯这里也是合适的,只要它们具有相当比例的上述范围内的射线即可。暴露时间通常为10秒至30分钟,优选2至15分钟。The graft copolymerization of the monomers applied to the activated surface can generally be initiated by radiation in the short-wave portion of the visible light range or in the long-wave portion of the UV range of electromagnetic radiation. For example, radiation from UV excimers with a wavelength of 250 to 500 nm, preferably 290 to 320 nm, is very suitable. Mercury vapor lamps are also suitable here as long as they have a substantial proportion of radiation in the above-mentioned range. The exposure time is usually 10 seconds to 30 minutes, preferably 2 to 15 minutes.

本发明共聚单体化合物的接枝共聚还可通过EP 0 872 512中描述的方法实现,并基于通过溶涨引入的单体分子和引发剂分子的接枝共聚。用于溶涨的单体可为组分II。The graft copolymerization of the comonomer compounds according to the invention can also be achieved by the method described in EP 0 872 512 and is based on the graft copolymerization of monomer molecules and initiator molecules introduced by swelling. The monomer used for swelling may be component II.

即使在基物表面上不接枝,上述通式的乙烯基醚(组分I),特别是3-氨丙基乙烯基醚,与至少一种脂族不饱和单体(组分II)的本发明抗微生物共聚物也呈现出杀微生物或抗微生物的性能。本发明的另一实施方案是将组分I和II在基物上进行共聚。Vinyl ethers of the general formula above (component I), especially 3-aminopropyl vinyl ether, with at least one aliphatically unsaturated monomer (component II), even without grafting on the substrate surface The antimicrobial copolymers of the present invention also exhibit microbicidal or antimicrobial properties. Another embodiment of the invention is the copolymerization of components I and II on a substrate.

可将这些组分以溶液形式施于基物上。合适的溶剂的例子是水、乙醇、甲醇、甲乙酮、二乙基醚、二噁烷、己烷、庚烷、苯、甲苯、氯仿、二氯甲烷、四氢呋喃和乙腈。还可将组分II用作组分I的溶剂。These components can be applied to the substrate in solution. Examples of suitable solvents are water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile. Component II can also be used as a solvent for component I.

本发明抗微生物共聚物也可直接使用,即不将这些组分在基物上聚合,而是作为抗微生物的涂层。合适的涂布方法是将这些共聚物以溶液形式或作为熔体涂布。The antimicrobial copolymers according to the invention can also be used directly, ie without polymerizing the components on the substrate, but as an antimicrobial coating. Suitable coating methods are coating these copolymers in solution or as a melt.

可将本发明聚合物的溶液通过,例如浸涂、喷涂或涂装涂于基材上。The solutions of the polymers according to the invention can be applied to the substrate by, for example, dipping, spraying or painting.

若本发明聚合物在不接枝下直接用于基物表面上,则可加入常规自由基引发剂。可用于制备本发明共聚物的引发剂的例子特别为偶氮腈、烷基过氧化物、氢过氧化物、酰基过氧化物、过氧酮、过酯、过氧碳酸盐、过二硫酸盐、过硫酸盐和任何通用光引发剂,如苯乙酮、α-羟基酮、二甲基缩酮和二苯甲酮。该聚合也可通过热引发,或如上所述通过电磁射线,如UV光或γ-射线引发。If the polymers according to the invention are used directly on the substrate surface without grafting, customary free-radical initiators can be added. Examples of initiators which can be used for the preparation of the copolymers according to the invention are in particular azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxyketones, peresters, peroxycarbonates, peroxodisulfuric acid salts, persulfates, and any common photoinitiators such as acetophenone, alpha-hydroxy ketones, dimethyl ketals, and benzophenones. The polymerization can also be initiated thermally or, as mentioned above, by electromagnetic radiation, such as UV light or gamma-rays.

本发明抗微生物聚合物还可用作配制油墨、漆或其它表面涂料的组分。改性聚合物基物的用途The antimicrobial polymers of the present invention may also be used as a component in the formulation of inks, paints or other surface coatings. Use of modified polymer bases

本发明还提供本发明抗微生物聚合物和共聚物用于生产抗微生物活性产品的用途,和按此方式生产的产品本身。这些产品可包含本发明改性的聚合物基物或由这些基物组成。这类产品优选基于用本发明聚合物表面改性的聚酰胺、聚氨酯、聚醚嵌段酰胺、聚酯酰胺或酰亚胺、PVC、聚烯烃、硅氧烷、聚硅氧烷、聚甲基丙烯酸酯或聚对苯二甲酸酯。The invention also provides the use of the antimicrobial polymers and copolymers of the invention for the production of antimicrobially active products, and the products produced in this way themselves. These products may comprise or consist of the modified polymeric substrates according to the invention. Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or imides, PVC, polyolefins, siloxanes, polysiloxanes, polymethyl Acrylate or Terephthalate.

这类抗微生物活性产品例如和特别为食品加工的机器部件,空调系统中的部件,屋顶,浴室和卫生间用物品,厨房物品,卫生装置的部件,用于动物笼子或房子的部件,娱乐产品,水系统的部件,食品包装物,装置的操作员控制台(触摸嵌板)和接触镜。Such antimicrobially active products are for example and especially for food processing machine parts, parts in air-conditioning systems, roofing, bathroom and toilet articles, kitchen articles, parts of sanitary installations, parts for animal cages or houses, recreational products, Components of the water system, food packaging, operator console (touch panel) and contact lenses of the unit.

本发明共聚物或接枝共聚物可用于其中重要性放在具有剥离性能(Antihafteigenschaften)的表面上或完全无细菌(即杀微生物)的表面上的任何领域。本发明共聚物或接枝聚合物的应用例子特别为涂料、保护漆和如下方面的其它涂料。The copolymers or graft copolymers according to the invention can be used in any field in which importance is placed on surfaces that have release properties (Antihafteigenschaften) or on surfaces that are completely bacteria-free (ie microbicidal). Examples of applications of the copolymers or graft polymers according to the invention are in particular paints, protective lacquers and other paints in the following respects.

·海洋:船壳、船坞、浮标、钻井平台、压载水仓Marine: ship hulls, docks, buoys, drilling platforms, ballast tanks

·建筑:屋顶、地基、墙壁、建筑物外观、温室、防晒、花园Construction: roofs, foundations, walls, building exteriors, greenhouses, sun protection, gardens

  围栏、木材防护Fences, wood protection

·卫生:公共厕所、浴室、淋浴帘、厕所物品、游泳池、桑拿Hygiene: Public toilets, bathrooms, shower curtains, toilet items, swimming pools, saunas

  浴、连接件、密封配料Baths, connectors, sealing ingredients

·日用必需品:机器、厨房、厨房物品、海绵垫、娱乐产品、Daily necessities: machines, kitchens, kitchen items, sponge pads, entertainment products,

  食品包装物、牛奶加工、饮水系统、化妆品Food packaging, milk processing, drinking water system, cosmetics

·机器部件:空调系统、离子交换器、水处理、太阳能装置、Machine components: air conditioning systems, ion exchangers, water treatment, solar installations,

  热交换器、生物反应器、膜Heat exchangers, bioreactors, membranes

·医用领域:接触镜、尿布、膜、植入物Medical field: contact lenses, diapers, membranes, implants

·消费者物品:汽车座椅、衣物(袜子、运动衣)、医院设备、Consumer goods: car seats, clothing (socks, sportswear), hospital equipment,

  门把手、电话听筒、公共交通工具、动物窝、现金出纳机、Doorknobs, telephone receivers, public transportation, animal shelters, cash registers,

  铺满整个地板的地毯、壁纸Carpet and wallpaper covering the entire floor

本发明还提供其表面已用本发明聚合物或方法改性的本发明聚合物基物用于生产卫生产品或医用技术中的物品的用途。上述所用优选材料同样适用。这类卫生产品的例子是牙刷、马桶座圈、梳子和包装材料。术语卫生物品还包括可在一定情况下与很多人接触的其它物体,如电话听筒、楼梯栏杆、门把手、窗户拉手、以及公共交通工具中的抓握带和抓握把手。医用技术中的物品的例子是导管、管子、保护或背衬膜,和外科装置。The invention also provides the use of polymer substrates according to the invention, the surfaces of which have been modified with polymers or processes according to the invention, for the production of hygiene products or articles in medical technology. The same applies to the preferred materials used above. Examples of such hygiene products are toothbrushes, toilet seats, combs and packaging materials. The term hygiene article also includes other objects which under certain circumstances come into contact with many people, such as telephone receivers, stair railings, door handles, window handles, and grip straps and grip handles in public transport. Examples of articles in medical technology are catheters, tubes, protective or backing films, and surgical devices.

给出下面的实施例以更详细地描述本发明,但不用于限制如专利的权利要求给出的范围。The following examples are given to describe the invention in more detail, but are not intended to limit the scope as given by the patent claims.

实施例1Example 1

将6g 3-氨丙基乙烯基醚(Aldrich)、6g甲基丙烯酸甲酯(Aldrich)和60ml乙醇加入三颈烧瓶中并在氩气流下加热至65℃。然后在搅拌下慢慢滴加入溶于4ml甲乙酮中的0.15g偶氮二异丁腈。将该混合物加热至70℃并在此温度下搅拌72h。反应结束后,将该反应混合物在搅拌下加入到0.5l去离子水中,由此沉淀出聚合物产品。过滤出产品后,将滤饼用100ml去离子水洗涤以除去仍然存在的单体残余物。然后将该产品在50℃下真空干燥24小时。6 g of 3-aminopropyl vinyl ether (Aldrich), 6 g of methyl methacrylate (Aldrich) and 60 ml of ethanol were charged into a three-necked flask and heated to 65°C under argon flow. Then, 0.15 g of azobisisobutyronitrile dissolved in 4 ml of methyl ethyl ketone was slowly added dropwise under stirring. The mixture was heated to 70 °C and stirred at this temperature for 72 h. After the reaction was complete, the reaction mixture was added to 0.5 l of deionized water with stirring, whereby the polymer product was precipitated. After filtering off the product, the filter cake was washed with 100 ml of deionized water to remove monomer residues still present. The product was then vacuum dried at 50°C for 24 hours.

实施例1a:Example 1a:

将0.05g来自实施例1的产品加入到20ml金黄色葡萄球菌(Staphylococcus aureus)的试验微生物悬浮液(Testkeimsuspension)中并振摇。接触时间15分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,再也检测不到金黄色葡萄球菌微生物。0.05 g of the product from Example 1 were added to 20 ml of a test microorganism suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, S. aureus microorganisms were no longer detectable.

实施例1b:Example 1b:

将0.05g来自实施例1的产品加入到20ml绿脓杆菌(Pseudomonas aeruginosa)的试验微生物悬浮液中并振摇。接触时间60分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,微生物数已从107降至1020.05 g of the product from Example 1 were added to 20 ml of a test microorganism suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, the microbial count had dropped from 10 7 to 10 2 .

实施例2Example 2

将6g 3-氨丙基乙烯基醚(Aldrich)、6g甲基丙烯酸丁酯(Aldrich)和60ml乙醇加入三颈烧瓶中并在氩气流下加热至65℃。然后在搅拌下慢慢滴加入溶于4ml甲乙酮中的0.15g偶氮二异丁腈。将该混合物加热至70℃并在此温度下搅拌72h。在这段时间结束后,将该反应混合物在搅拌下加入0.5l去离子水中,由此沉淀出聚合物产品。过滤出产品后,将滤饼用100ml去离子水洗涤以除去仍然存在的单体残余物。然后将该产品在50℃下真空干燥24小时。6 g of 3-aminopropyl vinyl ether (Aldrich), 6 g of butyl methacrylate (Aldrich) and 60 ml of ethanol were added to a three-necked flask and heated to 65 °C under argon flow. Then, 0.15 g of azobisisobutyronitrile dissolved in 4 ml of methyl ethyl ketone was slowly added dropwise under stirring. The mixture was heated to 70 °C and stirred at this temperature for 72 h. At the end of this period, the reaction mixture was added with stirring to 0.5 1 of deionized water, whereby the polymer product was precipitated. After filtering off the product, the filter cake was washed with 100 ml of deionized water to remove monomer residues still present. The product was then vacuum dried at 50°C for 24 hours.

实施例2a:Example 2a:

将0.05g来自实施例2的产品加入到20ml金黄色葡萄球菌的试验微生物悬浮液中并振摇。接触时间15分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,再也检测不到金黄色葡萄球菌微生物。0.05 g of the product from Example 2 was added to 20 ml of the test microorganism suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, S. aureus microorganisms were no longer detectable.

实施例2b:Example 2b:

将0.05g来自实施例2的产品加入到20ml绿脓杆菌的试验微生物悬浮液中并振摇。接触时间60分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,微生物数已从107降至1020.05 g of the product from Example 2 were added to 20 ml of the test microorganism suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, the microbial count had dropped from 10 7 to 10 2 .

实施例3Example 3

将6g 3-氨丙基乙烯基醚(Aldrich)、6g甲基丙烯酸2-二乙氨基乙酯(Aldrich)和60ml乙醇加入三颈烧瓶中并在氩气流下加热至65℃。然后在搅拌下慢慢滴加入溶于4ml甲乙酮中的0.15g偶氮二异丁腈。将该混合物加热至70℃并在此温度下搅拌72h。在这段时间结束后,将该反应混合物在搅拌下加入0.5l去离子水中,由此沉淀出聚合物产品。过滤出产品后,将滤饼用100ml去离子水洗涤以除去仍然存在的单体残余物。然后将该产品在50℃下真空干燥24小时。实施例3a:6 g of 3-aminopropyl vinyl ether (Aldrich), 6 g of 2-diethylaminoethyl methacrylate (Aldrich) and 60 ml of ethanol were added to a three-necked flask and heated to 65°C under argon flow. Then, 0.15 g of azobisisobutyronitrile dissolved in 4 ml of methyl ethyl ketone was slowly added dropwise under stirring. The mixture was heated to 70 °C and stirred at this temperature for 72 h. At the end of this period, the reaction mixture was added with stirring to 0.5 1 of deionized water, whereby the polymer product was precipitated. After filtering off the product, the filter cake was washed with 100 ml of deionized water to remove monomer residues still present. The product was then vacuum dried at 50°C for 24 hours. Example 3a:

将0.05g来自实施例3的产品加入到20ml金黄色葡萄球菌的试验微生物悬浮液中并振摇。接触时间15分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,微生物数已从107降到1020.05 g of the product from Example 3 was added to 20 ml of the test microorganism suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, the microbial count had dropped from 10 7 to 10 2 .

实施例3b:Example 3b:

将0.05g来自实施例3的产品加入到20ml绿脓杆菌的试验微生物悬浮液中并振摇。接触时间60分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,微生物数已从107降至1020.05 g of the product from example 3 was added to 20 ml of the test microorganism suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, the microbial count had dropped from 10 7 to 10 2 .

实施例4Example 4

将6g 3-氨丙基乙烯基醚(Aldrich)、6g甲基丙烯酸叔丁酯(Aldfich)和60ml乙醇加入三颈烧瓶中并在氩气流下加热至65℃。然后在搅拌下慢慢滴加入溶于4ml甲乙酮中的0.15g偶氮二异丁腈。将该混合物加热至70℃并在此温度下搅拌72h。在这段时间结束后,将该反应混合物在搅拌下加入0.5l去离子水中,由此沉淀出聚合物产品。过滤出产品后,将滤饼用100ml去离子水洗涤以除去仍然存在的单体残余物。然后将该产品在50℃下真空干燥24小时。6 g of 3-aminopropyl vinyl ether (Aldrich), 6 g of tert-butyl methacrylate (Aldfich) and 60 ml of ethanol were added to a three-necked flask and heated to 65 °C under argon flow. Then, 0.15 g of azobisisobutyronitrile dissolved in 4 ml of methyl ethyl ketone was slowly added dropwise under stirring. The mixture was heated to 70 °C and stirred at this temperature for 72 h. At the end of this period, the reaction mixture was added with stirring to 0.5 1 of deionized water, whereby the polymer product was precipitated. After filtering off the product, the filter cake was washed with 100 ml of deionized water to remove monomer residues still present. The product was then vacuum dried at 50°C for 24 hours.

实施例4a:Example 4a:

将0.05g来自实施例4的产品加入到20ml金黄色葡萄球菌的试验微生物悬浮液中并振摇。接触时间15分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,再也检测不到金黄色葡萄球菌微生物。0.05 g of the product from Example 4 was added to 20 ml of the test microorganism suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, S. aureus microorganisms were no longer detectable.

实施例4b:Example 4b:

将0.05g来自实施例4的产品加入到20ml绿脓杆菌的试验微生物悬浮液中并振摇。接触时间60分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,微生物数已从107降至102。实施例50.05 g of the product from Example 4 was added to 20 ml of the test microorganism suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, the microbial count had dropped from 10 7 to 10 2 . Example 5

将聚酰胺-12薄膜在压力1mbar下暴露于来自Heraeus的受激准分子辐射源的172nm射线中2分钟。将按此方式活化的薄膜在保护气氛下放入辐照反应器中并固定。然后在惰性气体对流下,将薄膜用6g3-氨丙基乙烯基醚(Aldrich)、6g甲基丙烯酸丁酯(Aldrich)和60g乙醇的20ml混合物覆盖。将辐射室密封并置于自在308nm波长处发射的Heraeus受激准分子辐照单元距离10cm处。辐照开始,时间为15分钟。然后将该薄膜取出并用30ml乙醇漂洗。然后将该薄膜在50℃下真空干燥12小时。接着将该薄膜在30℃下于水中在6小时内提取5次,然后在50℃下干燥12小时。The polyamide-12 film was exposed to 172 nm radiation from a Heraeus excimer radiation source for 2 minutes at a pressure of 1 mbar. The film activated in this way is placed in an irradiation reactor under a protective atmosphere and fixed. The film was then covered with a 20 ml mixture of 6 g 3-aminopropyl vinyl ether (Aldrich), 6 g butyl methacrylate (Aldrich) and 60 g ethanol under inert gas convection. The irradiation chamber was sealed and placed at a distance of 10 cm from a Heraeus excimer irradiation unit emitting at a wavelength of 308 nm. Irradiation starts and the time is 15 minutes. The film was then removed and rinsed with 30 ml of ethanol. The film was then vacuum dried at 50°C for 12 hours. The film was then extracted five times in water at 30° C. within 6 hours, and then dried at 50° C. for 12 hours.

然后将该薄膜的反面按此方式处理,这样最后获得的聚酰胺薄膜已在两面被接枝聚合物涂布。The opposite side of the film is then treated in such a way that the finally obtained polyamide film has been coated on both sides with the graft polymer.

实施例5a:Example 5a:

将来自实施例5的一片涂布薄膜(5×4cm)加入到30ml金黄色葡萄球菌的试验微生物悬浮液中并振摇。接触时间15分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,再也检测不到金黄色葡萄球菌微生物。One piece of coated film (5 x 4 cm) from Example 5 was added to 30 ml of the test microorganism suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, S. aureus microorganisms were no longer detectable.

实施例5b:Example 5b:

将来自实施例5的一片涂布薄膜(5×4cm)加入到30ml绿脓杆菌的试验微生物悬浮液中并振摇。接触时间60分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,微生物数已从107降至104One piece of coated film (5 x 4 cm) from Example 5 was added to 30 ml of the test microorganism suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, the microbial count had dropped from 10 7 to 10 4 .

实施例6Example 6

将聚酰胺-12薄膜在压力1mbar下暴露于来自Heraeus的受激准分子辐射源的172nm射线中2分钟。将按此方式活化的薄膜在保护气氛下放入辐照反应器中并固定。然后在保护气体对流下,将薄膜用6g3-氨丙基乙烯基醚(Aldrich)、6g甲基丙烯酸叔丁酯(Aldrich)和60g乙醇的20ml混合物覆盖。将辐射室密封并置于自在308nm波长处发射的Heraeus受激准分子辐照单元距离10cm处。辐照开始,时间为15分钟。然后将该薄膜取出并用30ml乙醇漂洗。将该薄膜在50℃下真空干燥12小时。接着将该薄膜在30℃下于水中在6小时内提取5次,然后在50℃下干燥12小时。The polyamide-12 film was exposed to 172 nm radiation from a Heraeus excimer radiation source for 2 minutes at a pressure of 1 mbar. The film activated in this way is placed in an irradiation reactor under a protective atmosphere and fixed. The film was then covered with a 20 ml mixture of 6 g 3-aminopropyl vinyl ether (Aldrich), 6 g tert-butyl methacrylate (Aldrich) and 60 g ethanol under protective gas convection. The irradiation chamber was sealed and placed at a distance of 10 cm from a Heraeus excimer irradiation unit emitting at a wavelength of 308 nm. Irradiation starts and the time is 15 minutes. The film was then removed and rinsed with 30 ml of ethanol. The film was vacuum dried at 50° C. for 12 hours. The film was then extracted five times in water at 30° C. within 6 hours, and then dried at 50° C. for 12 hours.

然后将该薄膜的反面按此方式处理,这样最后获得的聚酰胺薄膜已在两面被接枝聚合物涂布。The opposite side of the film is then treated in such a way that the finally obtained polyamide film has been coated on both sides with the graft polymer.

实施例6a:Example 6a:

将来自实施例6的一片涂布薄膜(5×4cm)加入到30ml金黄色葡萄球菌的试验微生物悬浮液中并振摇。接触时间15分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,再也检测不到金黄色葡萄球菌微生物。One piece of coated film (5 x 4 cm) from Example 6 was added to 30 ml of the test microorganism suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, S. aureus microorganisms were no longer detectable.

实施例6b:Example 6b:

将来自实施例6的一片涂布薄膜(5×4cm)加入到30ml绿脓杆菌的试验微生物悬浮液中并振摇。接触时间60分钟后,取出1ml试验的微生物悬浮液,并测定试验混合物中的微生物数。经此时间后,微生物数已从107降至104One piece of coated film (5 x 4 cm) from Example 6 was added to 30 ml of the test microorganism suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microorganism suspension was withdrawn and the number of microorganisms in the test mixture was determined. After this time, the microbial count had dropped from 10 7 to 10 4 .

Claims (22)

1.一种抗微生物共聚物,其通过将如下通式的乙烯基醚与至少一种脂族不饱和单体共聚获得,所述通式为:其中R1为具有1至5个碳原子的支化或未支化的烃基,和R2、R3为H、具有1至5个碳原子的支化或未支化的烃基,其中R2和R3可以相同或不同。1. An antimicrobial copolymer obtained by copolymerizing vinyl ethers of the following general formula with at least one aliphatic unsaturated monomer, said general formula being: Wherein R 1 is a branched or unbranched hydrocarbon group with 1 to 5 carbon atoms, and R 2 , R 3 are H, a branched or unbranched hydrocarbon group with 1 to 5 carbon atoms, wherein R 2 and R3 may be the same or different. 2.如权利要求1的抗微生物共聚物,其特征在于使用3-氨丙基乙烯基醚作为乙烯基醚。2. Antimicrobial copolymer according to claim 1, characterized in that 3-aminopropyl vinyl ether is used as vinyl ether. 3.如权利要求1或2的抗微生物聚合物,其特征在于脂族不饱和单体为甲基丙烯酸化合物。3. Antimicrobial polymer according to claim 1 or 2, characterized in that the aliphatically unsaturated monomer is a methacrylic compound. 4.如权利要求1或2的抗微生物聚合物,其特征在于脂族不饱和单体为丙烯酸化合物。4. Antimicrobial polymer according to claim 1 or 2, characterized in that the aliphatically unsaturated monomer is an acrylic compound. 5.如权利要求1或2的抗微生物聚合物,其特征在于使用的脂族不饱和单体为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸叔丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸叔丁酯、叔丁基氨基乙酯、甲基丙烯酸2-二乙氨基乙酯、2-二乙氨基乙基乙烯基醚、N-3-二甲氨基丙基甲基丙烯酰胺、3-甲基丙烯酰基氨丙基三甲基氯化铵、2-甲基丙烯酰氧基乙基三甲基氯化铵或2-甲基丙烯酰氧基乙基三甲基甲硫酸铵。5. The antimicrobial polymer according to claim 1 or 2, characterized in that the aliphatic unsaturated monomer used is methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate , methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butylaminoethyl, 2-diethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, N-3 -Dimethylaminopropylmethacrylamide, 3-methacryloylaminopropyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride or 2-methacryloyl Oxyethyltrimethylammonium Methosulfate. 6.如权利要求1至5中任何一项的抗微生物聚合物,其特征在于共聚在基物上进行。6. Antimicrobial polymer according to any one of claims 1 to 5, characterized in that the copolymerization is carried out on a substrate. 7.如权利要求1至5中任何一项的抗微生物聚合物,其特征在于共聚以基物接枝聚合进行。7. Antimicrobial polymer according to any one of claims 1 to 5, characterized in that the copolymerization is carried out as substrate graft polymerization. 8.如权利要求7的抗微生物聚合物,其特征在于在接枝聚合前将基物通过UV辐射、等离子体处理、电晕处理、火焰处理、臭氧处理、放电或γ-辐射活化。8. Antimicrobial polymer according to claim 7, characterized in that the substrate is activated by UV radiation, plasma treatment, corona treatment, flame treatment, ozone treatment, electric discharge or gamma-radiation before graft polymerization. 9.如权利要求7的抗微生物聚合物,其特征在于在接枝聚合前将基物通过使用光引发剂的UV辐射活化。9. Antimicrobial polymer according to claim 7, characterized in that the substrate is activated by UV radiation using a photoinitiator before the graft polymerization. 10.一种制备抗微生物共聚物的方法,其特征在于将如下通式的乙烯基醚与至少一种脂族不饱和单体共聚,所述通式为:其中R1为具有1至5个碳原子的支化或未支化的烃基,和R2、R3为H、具有1至5个碳原子的支化或未支化的烃基,其中R2和R3可以相同或不同。10. A method for preparing an antimicrobial copolymer, characterized in that vinyl ethers of the following general formula are copolymerized with at least one aliphatic unsaturated monomer, said general formula being: Wherein R 1 is a branched or unbranched hydrocarbon group with 1 to 5 carbon atoms, and R 2 , R 3 are H, a branched or unbranched hydrocarbon group with 1 to 5 carbon atoms, wherein R 2 and R3 may be the same or different. 11.如权利要求10的方法,其特征在于使用3-氨丙基乙烯基醚作为乙烯基醚。11. Process according to claim 10, characterized in that 3-aminopropyl vinyl ether is used as vinyl ether. 12.如权利要求10或11的方法,其特征在于脂族不饱和单体为甲基丙烯酸化合物。12. Process according to claim 10 or 11, characterized in that the aliphatically unsaturated monomer is a methacrylic compound. 13.如权利要求10或11的方法,其中脂族不饱和单体为丙烯酸化合物。13. A method as claimed in claim 10 or 11, wherein the aliphatically unsaturated monomer is an acrylic compound. 14.如权利要求10或11的方法,其中使用的脂族不饱和单体为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸叔丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸叔丁酯、叔丁基氨基乙酯、甲基丙烯酸2-二乙氨基乙酯、2-二乙氨基乙基乙烯基醚、N-3-二甲氨基丙基甲基丙烯酰胺、3-甲基丙烯酰基氨丙基三甲基氯化铵、2-甲基丙烯酰氧基乙基三甲基氯化铵或2-甲基丙烯酰氧基乙基三甲基甲硫酸铵。14. The method according to claim 10 or 11, wherein the aliphatic unsaturated monomer used is methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, methyl acrylate, Ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butylaminoethyl, 2-diethylaminoethyl methacrylate, 2-diethylaminoethyl vinyl ether, N-3-dimethylaminopropyl methacrylamide, 3-methacryloylaminopropyltrimethylammonium chloride, 2-methacryloyloxyethyltrimethylammonium chloride or 2-methacryloyloxyethyltrimethylammonium chloride Ammonium Methyl Methosulfate. 15.如权利要求10至14中任何一项的方法,其特征在于共聚在基物上进行。15. Process according to any one of claims 10 to 14, characterized in that the copolymerization is carried out on a substrate. 16.如权利要求10至14中任何一项的方法,其特征在于共聚以基物接枝聚合进行。16. Process according to any one of claims 10 to 14, characterized in that the copolymerization is carried out as a graft polymerization of the substrate. 17.如权利要求16的方法,其特征在于在接枝聚合前将基物通过UV辐射、等离子体处理、电晕处理、火焰处理、臭氧处理、放电或γ-辐射活化。17. The method according to claim 16, characterized in that the substrate is activated by UV radiation, plasma treatment, corona treatment, flame treatment, ozone treatment, electrical discharge or gamma-radiation before the graft polymerization. 18.如权利要求16的方法,其特征在于在接枝聚合前将基物通过使用光引发剂的UV辐射活化。18. The method according to claim 16, characterized in that the substrate is activated by UV radiation using a photoinitiator before the graft polymerization. 19.如权利要求1至9中任何一项的抗微生物聚合物用于生产具有抗微生物聚合物涂层的产品的用途。19. Use of an antimicrobial polymer according to any one of claims 1 to 9 for the production of a product with an antimicrobial polymer coating. 20.如权利要求1至9中任何一项的抗微生物聚合物用于生产具有抗微生物聚合物涂层的医用产品的用途。20. Use of an antimicrobial polymer according to any one of claims 1 to 9 for the production of a medical product with an antimicrobial polymer coating. 21.如权利要求1至9中任何一项的抗微生物聚合物用于生产具有抗微生物聚合物涂层的卫生物品的用途。21. Use of an antimicrobial polymer according to any one of claims 1 to 9 for the production of hygiene articles with an antimicrobial polymer coating. 22.如权利要求1至9中任何一项的抗微生物聚合物在表面涂层、保护漆或其它涂料中的用途。22. Use of an antimicrobial polymer according to any one of claims 1 to 9 in surface coatings, protective lacquers or other coatings.
CN00814780A 1999-08-24 2000-07-08 Copolymers of aminopropyl vinyl ether Pending CN1382164A (en)

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